JPH03240970A - Production of nonoriented silicon steel sheet excellent in film characteristic after stress relief annealing and surface treating agent therefor - Google Patents
Production of nonoriented silicon steel sheet excellent in film characteristic after stress relief annealing and surface treating agent thereforInfo
- Publication number
- JPH03240970A JPH03240970A JP3475390A JP3475390A JPH03240970A JP H03240970 A JPH03240970 A JP H03240970A JP 3475390 A JP3475390 A JP 3475390A JP 3475390 A JP3475390 A JP 3475390A JP H03240970 A JPH03240970 A JP H03240970A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- steel sheet
- resin
- annealing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000137 annealing Methods 0.000 title claims abstract description 53
- 229910000976 Electrical steel Inorganic materials 0.000 title claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 229920005989 resin Polymers 0.000 claims abstract description 77
- 239000011347 resin Substances 0.000 claims abstract description 77
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 41
- 239000010959 steel Substances 0.000 claims abstract description 41
- 229920001577 copolymer Polymers 0.000 claims abstract description 23
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 15
- 239000000839 emulsion Substances 0.000 claims abstract description 15
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 15
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 11
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 26
- 229910019142 PO4 Inorganic materials 0.000 claims description 16
- 235000021317 phosphate Nutrition 0.000 claims description 16
- 239000010419 fine particle Substances 0.000 claims description 15
- 229910000565 Non-oriented electrical steel Inorganic materials 0.000 claims description 13
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 12
- 238000009413 insulation Methods 0.000 claims description 12
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 10
- 229920000877 Melamine resin Polymers 0.000 claims description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000004793 Polystyrene Substances 0.000 claims description 10
- 229920002678 cellulose Polymers 0.000 claims description 10
- 239000001913 cellulose Substances 0.000 claims description 10
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 10
- 229920002223 polystyrene Polymers 0.000 claims description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 10
- 229920001296 polysiloxane Polymers 0.000 claims description 9
- 150000003440 styrenes Chemical class 0.000 claims description 9
- 239000012756 surface treatment agent Substances 0.000 claims description 9
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 8
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims description 8
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052725 zinc Inorganic materials 0.000 abstract description 5
- 239000011243 crosslinked material Substances 0.000 abstract 1
- 229920001519 homopolymer Polymers 0.000 abstract 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 abstract 1
- 239000004926 polymethyl methacrylate Substances 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 16
- 239000011575 calcium Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 9
- 239000011362 coarse particle Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 8
- 239000010452 phosphate Substances 0.000 description 8
- 230000003746 surface roughness Effects 0.000 description 7
- 229920000049 Carbon (fiber) Polymers 0.000 description 5
- 239000004917 carbon fiber Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000004080 punching Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229920000298 Cellophane Polymers 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 235000009470 Theobroma cacao Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 244000240602 cacao Species 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Heat Treatment Of Sheet Steel (AREA)
- Chemical Treatment Of Metals (AREA)
- Manufacturing Of Steel Electrode Plates (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、歪取焼鈍時の耐焼付き性に優れ、歪取焼鈍後
に滑り性および絶縁性に著しく優れた無方向性１１ｔ磁
鋼板の製造方法およびその製造方法に用いる電磁鋼抜用
表面処理剤に関するものである。Detailed Description of the Invention (Field of Industrial Application) The present invention is directed to the production of a non-oriented 11t magnetic steel sheet that has excellent seizure resistance during strain relief annealing and has extremely excellent slipperiness and insulation properties after strain relief annealing. The present invention relates to a method and a surface treatment agent for electromagnetic steel used in the manufacturing method.
（従来の技術）
電磁鋼板は、渦電流による鉄損を減少させるために、鋼
板表面に絶縁皮膜を塗布され、焼き付け処理が施されて
使用される。電磁鋼板が用いられるモーター或はトラン
スの鉄芯は、電磁鋼板或はストリップを所定の幅にスリ
ットした後、連続的に鉄芯形状に打ち抜くか切断した後
、積層し、この積層体のエツジ部を溶接によって或はカ
シメて固定するプロセスによって製作される。鉄芯は、
その後必要に応じて７００〜ｓ ｏ ｏ ’ｃの温度域
で歪取焼鈍を施された後、巻線がなされ、ケースに挿入
されて最終製品とされる。(Prior Art) In order to reduce iron loss caused by eddy currents, electrical steel sheets are used with an insulating film coated on the surface of the steel sheet and subjected to baking treatment. The iron core of a motor or transformer that uses electromagnetic steel sheets is made by slitting the electromagnetic steel sheets or strips to a predetermined width, then continuously punching or cutting them into the shape of the iron core, and then laminating them. It is manufactured by welding or caulking. The iron core is
Thereafter, if necessary, the wire is subjected to strain relief annealing in a temperature range of 700 to so'o'c, and then winding is performed and the wire is inserted into a case to form a final product.
従って、電磁鋼板表面に形成される絶縁皮膜は、絶縁性
に優れていることは勿論、密着性、打抜き性、耐熱性、
耐油性に優れるとともに電磁鋼板の占積率を低下せしめ
ないといった特性を有することが要求される。また、特
殊なケースとして、トランス用鉄芯或はＥＩココアよう
に、焼鈍後に再積層工程がある場合には、鋼板の滑り性
が積層作業の能率を左右するから、絶縁皮膜は、滑り性
に優れていることが併せ要求される。Therefore, the insulating film formed on the surface of the electromagnetic steel sheet not only has excellent insulation properties, but also has excellent adhesion, punchability, heat resistance, and
It is required to have characteristics such as excellent oil resistance and not reducing the space factor of the electrical steel sheet. In addition, as a special case, when there is a re-lamination process after annealing, such as for transformer iron cores or EI cocoa, the slipperiness of the steel plate affects the efficiency of the lamination work, so the insulation film should not be coated with slipperiness. Excellent qualities are also required.
絶縁皮膜に要求されるこれら特性を満足させるべく、種
々の絶縁皮膜形成方法が提案されてきている。−船釣に
は、１）燐酸塩またはクロム酸塩を主成分とする全無機
成分系の塗布剤を用いるもの、２）クロム酸塩をベース
とし、有機樹脂を添加配合する半有機成分系の塗布剤を
用いるもの、３）全量有機物からなる全有機成分系の塗
布剤を用いるもの、の３種類である。Various methods for forming an insulating film have been proposed in order to satisfy these characteristics required of an insulating film. -For boat fishing, 1) using a completely inorganic coating agent mainly consisting of phosphate or chromate; 2) using a semi-organic coating agent based on chromate with the addition of an organic resin; There are three types: 3) one that uses a coating agent, and 3) one that uses a coating agent that is entirely organic and consists entirely of organic substances.
１）の全熱ｍ成分系の塗布剤を用いる場合、耐熱性、溶
接性に優れた電磁鋼板を得ることができるけれども、打
抜き性、密着性が著しく劣る。When using the total heat m-component coating agent in 1), it is possible to obtain an electrical steel sheet with excellent heat resistance and weldability, but the punchability and adhesion are significantly inferior.
３）の全有機成分系の塗布剤を用いる場合、打抜き性、
密着性の良好な電磁鋼板とすることができるけれども、
耐熱性、溶接性が悪いという問題がある。3) When using an all-organic coating agent, punching properties,
Although it is possible to use electromagnetic steel sheets with good adhesion,
There are problems with poor heat resistance and weldability.
前記両者の欠点を補完すべく提案されているのが、２）
の半有機成分系の塗布剤を用いるものである。さらに最
近では、上記種々の絶縁皮膜形成方法の改善策が種々提
案されている。2) has been proposed to compensate for the shortcomings of both of the above.
A semi-organic coating agent is used. Furthermore, recently, various improvements to the above-mentioned various insulating film forming methods have been proposed.
一方、所定の形状に打抜き或は切断加工された鋼板の溶
接性を改善する手段として、鋼板表面を粗くすることが
特公昭４９−１９０７８号公報に提案されている。即ち
、
イ）有機皮膜を均一に塗布し、焼き付け中の未硬化皮膜
に、粗面を有するロールを接触させ、粗面を有する絶縁
皮膜とする方法、
口）溝切り塗布ロールで鋼板表面に縦溝皮膜を形威し、
次いで焼き付け中の未硬化皮膜に、溝を刻設した鋼製ロ
ールを接触させ、鋼板幅方向に延在する溝を入れる方法
、
ハ）塗布剤中に、約２μ階以上の粒径を有する有機物粒
子を添加して鋼板に塗布し、焼付ける方法、
の３つの手段が提案されている。On the other hand, as a means to improve the weldability of a steel plate that has been punched or cut into a predetermined shape, it has been proposed in Japanese Patent Publication No. 19078/1987 to roughen the surface of the steel plate. That is, a) A method of uniformly applying an organic film and bringing a roll with a rough surface into contact with the uncured film during baking to form an insulating film with a rough surface. The groove film is shaped,
Next, a steel roll with grooves is brought into contact with the uncured film being baked to form grooves extending in the width direction of the steel sheet; c) an organic substance having a particle size of about 2 μm or more in the coating agent; Three methods have been proposed: a method in which particles are added, applied to a steel plate, and baked.
また、特公昭５５−２１１１１号公報には、有機物粒子
の分散性および鋼板への付着性を向上させる手段として
、鋼板表面に燐酸系乃至クロム酸系の一種または二種を
有機樹脂と混合するに際し、塗布剤中に有機樹脂粒子を
混合することによって、２〜１０ Ｑ （Ｈｍａｘ）の
表面粗さをもつ、打抜き性、溶接性に優れた電気絶縁皮
膜を有する電磁鋼板を得る方法であって、５−の径をも
つ有機樹脂粒子を予めエマルジョン樹脂溶液に添加して
均一に分散させた後、この溶液を上記無機物ｉｔ温溶液
混合して電磁鋼板表面に塗布し、次いで４００〜７００
°Ｃの温度域で短時間の焼き付け処理を施すことによっ
て上記樹脂を一部溶融してその付着力を向上させる技術
が開示されている。In addition, Japanese Patent Publication No. 55-21111 discloses that as a means to improve the dispersibility of organic particles and their adhesion to steel sheets, one or two types of phosphoric acid or chromic acid are mixed with an organic resin on the surface of the steel sheet. , a method for obtaining an electrical steel sheet having an electrically insulating film having a surface roughness of 2 to 10 Q (Hmax) and excellent punchability and weldability by mixing organic resin particles in a coating agent, Organic resin particles having a diameter of 400 to 700 mm are added in advance to an emulsion resin solution and dispersed uniformly, and this solution is mixed with the above-mentioned inorganic material and applied to the surface of an electrical steel sheet.
A technique has been disclosed in which the above-mentioned resin is partially melted by performing a short-time baking treatment in a temperature range of .degree. C. to improve its adhesion.
耐焼鈍性を改善する手段として、燐酸、クロム酸、硼酸
、チオ結合を有する水溶性有機化合物および明欝を混合
した処理液を電磁鋼板に塗布する方法が、特公昭５５−
１３４８号公報に開示されている。As a means to improve annealing resistance, a method was proposed in the Japanese Patent Publication No. 1983-1999 in which a treatment solution containing a mixture of phosphoric acid, chromic acid, boric acid, a water-soluble organic compound having a thio bond, and alum was applied to electrical steel sheets.
It is disclosed in Japanese Patent No. 1348.
この先行技術によるときは、焼鈍後の’ａｍ鋼板の電気
絶縁性はかなり改善されるけれども、打抜き性が十分で
はない。According to this prior art, although the electrical insulation properties of the 'am steel plate after annealing are considerably improved, the punchability is not sufficient.
このように、従来の有機或は半有機系絶縁皮膜に関して
は、有機物から発生するガスによる溶接性の低下を抑え
ることに主眼が置かれ、そのために、鋼板間における通
気性を良好ならしめるべく、皮膜表面粗さを大きくする
ことに努力が払われてきた。As described above, the main focus of conventional organic or semi-organic insulating films is to suppress the deterioration of weldability due to gases generated from organic substances, and for this purpose, in order to improve the air permeability between steel plates, Efforts have been made to increase film surface roughness.
しかしながら、従来の有機或は半有機系絶縁皮膜は、有
機物の耐熱性が高々４００〜５００°Ｃである。従って
、電磁鋼板の需要家における歪取焼鈍のように、７００
〜ｓ ｏ ｏ ’ｃの温度域での高温熱処理を電磁鋼板
に施すと、有機物は焼失してしまう。However, in conventional organic or semi-organic insulating films, the heat resistance of the organic material is at most 400 to 500°C. Therefore, as in strain relief annealing for electromagnetic steel sheet customers, 700
When an electrical steel sheet is subjected to high-temperature heat treatment in a temperature range of ~so'c, organic matter is burned out.
前記のように、従来の粗粒樹脂を用いる技術は、乾燥、
焼き付け処理時に樹脂粒子の一部溶融によって皮膜を半
溶融状態にして、焼き付け後にある程度の表面粗さを有
せしめるようにしたものであり、従来、粗粒樹脂の耐熱
性や焼鈍後の＼効果に着目した研究はなされていない。As mentioned above, conventional techniques using coarse-grained resin require drying,
The coating is made into a semi-molten state by partially melting the resin particles during the baking process, so that it has a certain degree of surface roughness after baking. No research has focused on this.
かかる状況から、有機或は半有機系絶縁皮膜に関しては
、皮膜の耐熱性を向上させて焼鈍時の皮膜耐焼付き性や
焼鈍後の皮膜特性を改良する技術の開発が強く望まれて
いた。Under these circumstances, with regard to organic or semi-organic insulating films, there has been a strong desire to develop a technology that improves the heat resistance of the film and improves the film seizure resistance during annealing and the film properties after annealing.
（発明が解決しようとする課題）
本発明は、従来技術における皮膜特性を損なうことなく
、電磁鋼板（鉄芯）の歪取焼鈍時の耐スティッキング性
、焼鈍後の鋼板滑り性、耐食性。(Problems to be Solved by the Invention) The present invention aims to improve the sticking resistance during strain relief annealing of electrical steel sheets (iron cores), the slipperiness of the steel sheet after annealing, and the corrosion resistance, without impairing the film properties in the prior art.
電気絶縁性に優れた絶縁皮膜を得ることができる無方向
性電磁鋼板の製造方法およびその方法に用いる電ｍａ板
用表面処理剤を提供することを目的とするものである。The object of the present invention is to provide a method for manufacturing a non-oriented electrical steel sheet that can obtain an insulating film with excellent electrical insulation properties, and a surface treatment agent for electrical steel sheets used in the method.
（課題を解決するための手段） 本発明の要旨とするところは下記のとおりである。(Means for solving problems) The gist of the present invention is as follows.
（１） ＣｒＯ＋ １００重量部、／Ｖ、 Ｍｇ、
Ｃａ、 Ｚｎから選ばれる酸化物の一種又は二種以上２
０〜４０重量部、粒子径０．２〜０．５ μｍに調整し
たアクリル、スチレン、酢酸ビニル及び／又はこれらの
共重合体からなる樹脂の一種又は二種以上の微粒子エマ
ルジョン溶液１０〜６０重量部（固形分換算）、粒子径
を１〜５０μｍに調整したメチルメタアクリレートポリ
アクリルニトリル，ポリスチレン、スルホン化スチレン
、セルローズ、シリコン、メラミン、フェノール、ポバ
ールの樹脂及び／又はこれらの共重合体、架橋体の一種
又は二種以上２〜３０重量部からなる電磁鋼板用表面処
理剤。(1) CrO+ 100 parts by weight, /V, Mg,
One or more oxides selected from Ca and Zn2
0 to 40 parts by weight, 10 to 60 parts by weight of a fine particle emulsion solution of one or more resins made of acrylic, styrene, vinyl acetate and/or copolymers thereof, adjusted to a particle size of 0.2 to 0.5 μm. (solid content equivalent), methyl methacrylate polyacrylonitrile, polystyrene, sulfonated styrene, cellulose, silicone, melamine, phenol, poval resins and/or copolymers thereof, crosslinked, with particle diameter adjusted to 1 to 50 μm. A surface treatment agent for electrical steel sheets comprising 2 to 30 parts by weight of one or more types.
（２） ＣｒＯ＋ １００重量部、Ａｊ、 Ｍｇ、
Ｃａ、 Ｚｎから選ばれる酸化物の一種又は二種以上２
０〜４０重量部、ｋｌ、 Ｍｇ、 Ｃａから選ばれる第
一燐酸塩の一種又は二種以上５〜２５重量部、粒子径０
．２〜０．５μｍに調整したアクリル、スチレン、酢酸
ビニル及び／又はこれらの共重合体からなる樹脂の一種
又は二種以上の微粒子エマルジョン溶液１０〜６０重量
部（固形分換算）、粒子径１〜５０Ｉｎμｍに調整した
メチルメタアクリレートポリアクリルニトリル，ポリス
チレン、スルホン化スチレン、セルローズ、シリコン、
メラミン、フェノール、ポバールの樹脂及び／又はこれ
らの共重合体、架橋体の一種又は二種以上２〜３０重量
部からなる電磁鋼板用表面処理剤。(2) CrO+ 100 parts by weight, Aj, Mg,
One or more oxides selected from Ca and Zn2
0 to 40 parts by weight, 5 to 25 parts by weight of one or more primary phosphates selected from Kl, Mg, and Ca, particle size 0
．． A fine particle emulsion solution of one or more resins made of acrylic, styrene, vinyl acetate, and/or their copolymers adjusted to 2 to 0.5 μm, 10 to 60 parts by weight (in terms of solid content), particle size 1 to Methyl methacrylate polyacrylonitrile adjusted to 50 In μm, polystyrene, sulfonated styrene, cellulose, silicon,
A surface treatment agent for electrical steel sheets comprising 2 to 30 parts by weight of one or more of melamine, phenol, and poval resins and/or copolymers and crosslinked products thereof.
（３）無方向性ｔＴ６１ｍ板用素材板金素材方法で処理
し、最終焼鈍を行った鋼板上にクロム酸及び／又はクロ
ム酸塩の一種又は二種以上と有機樹脂からなる無機−有
機系皮膜の焼き付け処理を施す無方向性電磁鋼板の製造
方法において、ＣｒＯ３１００重量部、ｌ’Ｊ、 Ｍｇ
＋ Ｃａ＋ Ｚｎから選ばれる酸化物の一種又は二種以
上２０〜４０重量部、粒子径０．２〜０、５ μｍに調
整したアクリル、スチレン、酢酸ビニル及び／又はこれ
らの共重合体からなる樹脂の一種又は二種以上の微粒子
エマルジョン溶液１０〜６０重量部（固形分換算）、粒
子径１〜５０μｍに調整したメチルメタアクリレートポ
リアクリルニトリル，ポリスチレン、スルホン化スチレ
ン。(3) Material for non-directional tT61m plate An inorganic-organic film consisting of one or more types of chromic acid and/or chromates and an organic resin is applied to a steel plate treated with the sheet metal material method and finally annealed. In a method for manufacturing a non-oriented electrical steel sheet that undergoes baking treatment, 100 parts by weight of CrO, l'J, Mg
+ Ca + 20 to 40 parts by weight of one or more oxides selected from Zn, a resin made of acrylic, styrene, vinyl acetate, and/or a copolymer thereof adjusted to a particle size of 0.2 to 0.5 μm 10 to 60 parts by weight (in terms of solid content) of a fine particle emulsion solution of one or more of the following, methyl methacrylate polyacrylonitrile, polystyrene, and sulfonated styrene adjusted to a particle size of 1 to 50 μm.
セルローズ、シリコン、メラミン、フェノール。Cellulose, silicone, melamine, phenol.
ポバールの樹脂及び／又はこれらの共重合体、架橋体の
一種又は二種以上２〜３０重量部からなる表面処理剤を
塗布し、焼き付け処理することを特徴とする歪み取り焼
鈍時の耐焼付き性が優れ、焼鈍後の潤滑性及び絶縁性の
著しく優れる無方向性電磁鋼板の製造方法。Seizure resistance during strain relief annealing characterized by applying a surface treatment agent consisting of 2 to 30 parts by weight of one or more of Poval resin and/or their copolymers and crosslinked products and baking treatment. A method for producing a non-oriented electrical steel sheet that has excellent lubricity and insulation properties after annealing.
（４）無方向検電ＷＬｗ４板用素材を公知の方法で処理
し、最終焼鈍を行った鋼板上にクロム酸及び／又はクロ
ム酸塩の一種又は二種以上と有機樹脂からなる無機−有
機系皮膜の焼き付け処理を施す無方向性電磁鋼板の製造
方法において、Ｃｒ（ｈ １００重量部、ｊＶ、 Ｆｌ
ｇ、 Ｃａ、 Ｚｎから選ばれる酸化物の一種又は二種
以上２０〜４０重量部、Ａｊ、 Ｍｇ、 Ｃａから選ば
れる第一燐酸塩の一種又は二種以上５〜２５重量部、粒
子径０．２〜０．５ｍに調整したアクリル、スチレン、
酢酸ビニル及び／又はこれらの共重合体からなる樹脂の
一種又は二種以上の微粒子エマルジョン溶液１０〜６０
重量部（固形分換算）、粒子径１〜５０Ｉｒｍに調整し
たメチルメタアクリレートポリアクリルニトリル，ポリ
スチレン、スルホン化スチレン、セルローズ、シリコン
、メラ逅ン、フェノール、ポバールの樹脂及び／又はこ
れらの共重合体、架橋体の一種又は二種以上２〜３０重
量部からなる表面処理剤を塗布し、焼き付け処理をする
ことを特徴とする歪み取り焼鈍時の耐焼付き性が優れ、
焼鈍後の潤滑性及び絶縁性の著しく優れる無方向性電磁
鋼板の製造方法。(4) An inorganic-organic system consisting of one or more types of chromic acid and/or chromate salts and an organic resin on a steel plate that has been processed by a known method and finally annealed. In a method for manufacturing a non-oriented electrical steel sheet in which a film is baked, Cr (h 100 parts by weight, jV, Fl
20 to 40 parts by weight of one or more oxides selected from Aj, Ca, and Zn, 5 to 25 parts by weight of one or more primary phosphates selected from Aj, Mg, and Ca, and a particle size of 0. Acrylic, styrene, adjusted to 2-0.5m.
Fine particle emulsion solution of one or more resins made of vinyl acetate and/or copolymers thereof 10 to 60
Resins of methyl methacrylate polyacrylonitrile, polystyrene, sulfonated styrene, cellulose, silicone, melamine, phenol, poval and/or copolymers thereof adjusted to a particle size of 1 to 50 Irm by weight part (solid content equivalent) , has excellent seizure resistance during strain relief annealing, which is characterized by applying a surface treatment agent consisting of 2 to 30 parts by weight of one or more crosslinked bodies and performing a baking treatment,
A method for producing a non-oriented electrical steel sheet that has extremely excellent lubricity and insulation properties after annealing.
以下に、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明者等は、電気機器加工メーカーのニーズに応える
べく、無方向性電磁鋼板を使用する膨大な実験と研究を
重ねた結果、上記従来の改良技術を以てしても解決でき
なかった有機−無機成分系皮膜の焼鈍後の特性上の問題
、わけても焼鈍時における皮膜の耐焼付き性（耐ステイ
ツキング性）、焼鈍後の鋼板の滑り性、耐食性、を気絶
練性の問題を一挙に解決し得る技術を開発することに成
功した。In order to meet the needs of electrical equipment processing manufacturers, the present inventors have conducted extensive experiments and research using non-oriented electrical steel sheets. As a result, we have found that the organic-inorganic Problems with the properties of component-based films after annealing, especially the seizure resistance of the film during annealing, the slipperiness of the steel plate after annealing, corrosion resistance, and stun kneading problems can be solved all at once. succeeded in developing the technology.
即ち、本発明においては、有機−無機系皮膜の成分中に
、７００〜ｓ ｏ ｏ ”ｃといった高温の熱処理を電
磁鋼板（鉄芯）に施すと、カーボンファイバーを形成し
たり、ベース樹脂との反応物を形成するような高耐熱性
タイプの粗粒樹脂を、一定の粒子形態と添加量で配合す
ることによって、従来技術における問題を解決し得るこ
とを新に見出した。That is, in the present invention, when an electromagnetic steel sheet (iron core) is subjected to high-temperature heat treatment of 700 to s o o ”c in the components of the organic-inorganic coating, carbon fibers are formed and the bond with the base resin is formed. It has been newly discovered that the problems in the prior art can be solved by blending a highly heat-resistant type coarse-grained resin that forms a reactant with a certain particle form and addition amount.
本発明においては、第一に、クロム酸塩−有機樹脂系皮
膜において、皮膜成分として特定の耐熱型の粗粒樹脂を
添加配合することにより、熱処理時にこの樹脂分或いは
共重合或いは架橋反応物をカーボンファイバー化して残
留させて表面の形状をコンｌ−’Ｅ−ルする。この表面
形状効果により、焼鈍時の皮膜同士の焼付きを防止した
り焼鈍後の潤滑性や絶縁性を向上することができる。第
二に、無機成分として、燐酸Ｃａ等の燐酸塩を併用して
微量添加することにより、焼鈍後の潤滑性や耐食性を向
上させるものである。In the present invention, firstly, by adding and blending a specific heat-resistant coarse-grained resin as a coating component in the chromate-organic resin coating, this resin content or copolymerization or crosslinking reaction product is removed during heat treatment. It is made into carbon fiber and left to control the surface shape. This surface shape effect can prevent the films from sticking to each other during annealing and improve the lubricity and insulation properties after annealing. Second, by adding a small amount of phosphate such as Ca phosphate as an inorganic component, the lubricity and corrosion resistance after annealing are improved.
特に、耐熱型の粗粒樹脂と微量の燐酸塩を併用した場合
には、微粒子の樹脂分の中に点在する耐熱性粗粒子樹脂
と微量燐酸塩の存在によって通常の半有機皮膜では熱処
理時に生じる皮膜の分解亀裂が抑制されるため、焼鈍後
の耐食性が著しく改善される。このような効果は、通常
の有機樹脂では全く得られず、本発明の範囲の特定の樹
脂とその形状で、微量燐酸塩を併用した時に効果が増大
するものである。In particular, when a heat-resistant coarse-grained resin and a trace amount of phosphate are used together, the presence of the heat-resistant coarse-grained resin and trace amount of phosphate dotted within the fine-particle resin makes it difficult for ordinary semi-organic coatings to be applied during heat treatment. Since decomposition cracks in the film that occur are suppressed, corrosion resistance after annealing is significantly improved. Such effects cannot be obtained at all with ordinary organic resins, but the effects are enhanced when a specific resin within the scope of the present invention and its shape are used together with a trace amount of phosphate.
本発明に使用する処理液の種類及び配合割合及び処理条
件を前記範囲にするのが好適であるのは、以下の理由に
よる。The reason why it is preferable to keep the type and blending ratio of the treatment liquid used in the present invention, the mixing ratio, and the treatment conditions within the above ranges is as follows.
本発明に使用する処理剤は主成分として第一にクロム酸
と、Ａｌ， Ｍｇ、 Ｃａ、 Ｚｎから選ばれる酸化物
の一種又は二種以上と、必要に応してｋｌ、 Ｍｇ、
Ｃａから選ばれる第一燐酸塩の一種または二種以上が添
加された溶液が無機成分として使用される。The treatment agent used in the present invention has as main components first chromic acid, one or more oxides selected from Al, Mg, Ca, and Zn, and optionally Kl, Mg,
A solution containing one or more primary phosphates selected from Ca is used as the inorganic component.
第二に有機成分としては粒子径を０．２〜０．５四に調
整したアクリル、スチレン、酢酸ビニル及びこれらの共
重合体の一種又は二種以上を添加配合させたものが主成
分である。Second, the main organic component is a mixture of acrylic, styrene, vinyl acetate, and one or more of these copolymers with particle diameters adjusted to 0.2 to 0.54. .
本発明では、第三の構成物として粒子径を１〜５０即に
調整したメチルメタアクリレートポリアクリルニトリル
，ポリスチレン、スルホン化スチレン、セルローズ、シ
リコン、メラミン、フェノール、ポバールの樹脂及び／
又はこれらの共重合体、架橋体の一種又は二種以上が添
加剤として使用される。In the present invention, the third component is a resin of methyl methacrylate polyacrylonitrile, polystyrene, sulfonated styrene, cellulose, silicone, melamine, phenol, poval and/or a resin whose particle size is adjusted to 1 to 50.
Alternatively, one or more of these copolymers and crosslinked products are used as additives.
即ち、従来の技術としてのクロム酸−クロム酸塩−微粒
子有機エマルジョン処理剤に対し、クロム酸及びｊＶ、
Ｍｇ、 Ｃａ、 Ｚｎから選ばれる酸化物の一種又は
二種以上−必要に応してＡｊ、 Ｍｇ、 Ｃａから選ば
れる第一燐酸塩の一種または二種以上−微粒子樹脂エマ
ルジョン溶液−粗粒子耐熱性樹脂によって構成されると
ころに特徴がある。That is, in contrast to the conventional chromic acid-chromate-fine particle organic emulsion treatment agent, chromic acid and jV,
One or more oxides selected from Mg, Ca, and Zn - If necessary, one or more primary phosphates selected from Aj, Mg, and Ca - Fine particle resin emulsion solution - Coarse particle heat resistance It is unique in that it is made of resin.
第一の無機成分としては、ＣｒＯ３１００重量部に対し
、ｊＶ、 Ｍｇ、 Ｃａ、 Ｚｎから選ばれる酸化物の
一種又は二種以上２０〜４０重量部と、必要に応じてＩ
ｋＪ、 Ｍｇ、 Ｃａから選ばれる第一燐酸塩の一種ま
たは二種以上５〜２５重量部とが配合される。この無機
成分は皮膜中のＣｒ”の還元や皮膜の密着性、耐熱性等
をコントロールするために重要である。As the first inorganic component, based on 100 parts by weight of CrO3, 20 to 40 parts by weight of one or more oxides selected from jV, Mg, Ca, and Zn, and if necessary, I
5 to 25 parts by weight of one or more primary phosphates selected from kJ, Mg, and Ca are blended. This inorganic component is important for controlling the reduction of Cr'' in the film and the adhesion, heat resistance, etc. of the film.
ＣｒＯ３に対する酸化物の量が２０重量部未満ではフリ
ーのＣｒ″６が増加し、必要以上の還元剤の添加を必要
とするため好ましくない。逆に４０重量部超では酸化物
によってはＣｒＯ、と反応しないフリーの酸化物が残留
するため、皮膜外観や密着性を損ねるため好ましくない
。If the amount of oxide is less than 20 parts by weight with respect to CrO3, free Cr''6 will increase, making it necessary to add more reducing agent than necessary, which is not preferable.On the other hand, if it exceeds 40 parts by weight, some oxides may become CrO. This is not preferred because unreacted free oxides remain, impairing the appearance and adhesion of the film.
無機成分として必要に応じて添加される前記第一燐酸塩
は５〜２５重量部が配合される。５重量部未満では焼鈍
後の耐熱性や潤滑性、耐食性の改善効果が小さく、２５
重量部超では、打抜き性、密着性に悪影響を与える。前
記第一燐酸塩は耐熱型の有機樹脂成分等との反応でつく
りだす表面の微細な凹凸形状の形成に効果的であり、特
に、第一燐酸カルシウムの添加よる皮膜の潤滑特性の向
上効果は顕著である。The primary phosphate, which is added as an inorganic component if necessary, is blended in an amount of 5 to 25 parts by weight. If it is less than 5 parts by weight, the effect of improving heat resistance, lubricity, and corrosion resistance after annealing will be small;
If the amount exceeds the weight part, punching performance and adhesion will be adversely affected. The monobasic phosphate is effective in forming fine irregularities on the surface by reaction with heat-resistant organic resin components, etc., and in particular, the effect of improving the lubricating properties of the film by adding calcium monophosphate is remarkable. It is.
次に第二の主成分である微粒子有機樹脂としてのアクリ
ル、スチレン、酢酸ビニル及び／又はこれらの共重合体
からなる樹脂の一種または二種以上の微粒子エマルジョ
ン溶液の配合割合はＣｒ０３１００重量部に対し１０〜
６０重量部（固形分換算）である。この限定条件は、打
抜き性、溶接性、等の特性に影響を与えるため重要で、
１０重量部より少ないと打抜き性が極端に劣化する。逆
に６０重量部超では溶接性と耐熱性が劣化するため好ま
しくない。しかして、前記微粒子有機樹脂の粒子径は０
．２〜０．５ｎの微粒子であることが重要である。この
粒子径は、後述する第三の有機樹脂成分と第一の無機成
分との乾燥或いは熱処理時の反応によって焼き付け処理
後に鋼板表面形状が微妙に造り出され、焼鈍前後の潤滑
性等の改善効果を生じると共に、耐熱性の良い皮膜を形
成するために重要である。０．５ｎより大きいとｙｌ塗
りした場合に外観の良い皮膜が得られず、又、占積率を
悪くする。他方、０．２−未満では安定して十分な分散
性のあるエマルジョン樹脂溶液を工業的に得るのが困難
である。Next, the blending ratio of the fine particle emulsion solution of one or more resins consisting of acrylic, styrene, vinyl acetate and/or their copolymers as the second main component as a fine particle organic resin is based on 100 parts by weight of Cr03. 10～
It is 60 parts by weight (in terms of solid content). This limiting condition is important because it affects properties such as punchability and weldability.
If it is less than 10 parts by weight, punching performance will be extremely poor. On the other hand, if it exceeds 60 parts by weight, weldability and heat resistance deteriorate, which is not preferable. However, the particle size of the fine particle organic resin is 0.
．． It is important that the particle size is 2 to 0.5n. This particle size is determined by the reaction during drying or heat treatment between the third organic resin component and the first inorganic component, which will be described later, to create a delicate surface shape of the steel sheet after baking, and to improve the lubricity before and after annealing. It is important for forming a film with good heat resistance. If it is larger than 0.5n, it will not be possible to obtain a film with good appearance when yl coating is performed, and the space factor will be deteriorated. On the other hand, if it is less than 0.2, it is difficult to industrially obtain a stable emulsion resin solution with sufficient dispersibility.
第三の構成成分である粗粒耐熱性の樹脂としては、粒子
径が１〜５０ｎのメチルメタアクリレートポリアクリル
ニトリル，ポリスチレン、スルホン化スチレン、セルロ
ーズ、シリコン、メラミン、フェノール、ポバールの樹
脂及び／又はこれらの共重合体、架構体樹脂の一種又は
二種以上が使用される。The coarse heat-resistant resin that is the third component includes methyl methacrylate polyacrylonitrile, polystyrene, sulfonated styrene, cellulose, silicone, melamine, phenol, poval resin and/or resin with a particle size of 1 to 50 nm. One or more of these copolymers and frame resins may be used.
これらの樹脂は、焼鈍によって樹脂分のカーボンファイ
バー化が生じ、ヘース樹脂や燐酸塩との反応物によって
、鋼板表面に緻密なカーボンファイバー主成分の突起を
残留させて焼鈍後の表面形状のコントロールを可能にす
る。When these resins are annealed, the resin content turns into carbon fibers, and the reactants with Heas resin and phosphates leave dense protrusions mainly composed of carbon fibers on the surface of the steel sheet, allowing control of the surface shape after annealing. enable.
粗粒樹脂の効果は前記樹脂のいずれでもそれなりの効果
は得られるが、前記樹脂の共重合体もしくは架橋体を使
用するか、これらを組合せて使用した場合が最も効果的
である。While any of the above-mentioned resins can provide a certain effect as a coarse-grained resin, it is most effective when a copolymer or crosslinked product of the above-mentioned resins is used, or when these are used in combination.
粗粒樹脂の粒子径は１〜５０ｍとする。Ｉｎより小さい
と焼鈍後のファイバー状突起による目的の粗さが得られ
ず、またベース皮膜成分の焼鈍による亀裂発生の防止効
果が得られない。このため、潤滑性、絶縁性等の向上効
果が得られない。The particle diameter of the coarse resin is 1 to 50 m. If it is smaller than In, the desired roughness due to the fibrous protrusions after annealing cannot be obtained, and the effect of preventing the occurrence of cracks due to annealing of the base film component cannot be obtained. Therefore, the effect of improving lubricity, insulation, etc. cannot be obtained.
５０、ｎより大きいと、カーボンファイバー主成分の突
起が大きくなり過ぎて占積率を劣化させるため好ましく
ない。If it is larger than 50.n, the protrusions of the carbon fiber main component become too large, which deteriorates the space factor, which is not preferable.
粗粒樹脂の配合割合はＣｒＯ、 １００重量部に対し２
〜３０重量部である。２重量部より少ないと焼鈍後に目
的の表面の微細な凹凸形状は得られず、潤滑性、耐ステ
イツキング性の改善や皮膜の緻密化が生じない。３０重
量部より多いと表面粗さが粗くなり過ぎて占積率が劣化
するため問題である。The blending ratio of coarse particle resin is 2 to 100 parts by weight of CrO.
~30 parts by weight. If the amount is less than 2 parts by weight, the desired fine surface unevenness cannot be obtained after annealing, and the lubricity and staking resistance will not be improved and the film will not be densified. If the amount is more than 30 parts by weight, the surface roughness becomes too rough and the space factor deteriorates, which is a problem.
第１図に粗粒樹脂の種類と添加量の歪取焼鈍後の鋼板の
表面粗さＲａとの関係を示す。この結果でも粗粒樹脂の
単体物よりも、共重合体を使用した場合の方が焼鈍後の
Ｒａ値が大きく、耐熱性の良い結果が得られている。FIG. 1 shows the relationship between the type and amount of coarse grain resin added and the surface roughness Ra of the steel plate after strain relief annealing. This result also shows that the Ra value after annealing is larger when the copolymer is used than when the coarse particle resin is used as a single substance, and good heat resistance is obtained.
第２図には、ＣｒＯ＋１００ ｇ ＋ＭｇＯ２０ｇ＋微
粒子アクリル−スチレン樹脂エマルジョンからなるベー
ス液に、耐熱性粗粒樹脂として粒子径２５ｎのメチルメ
タアクリレートの添加量を変えて添加した場合の焼鈍後
の潤滑性を測定した結果を示す。Figure 2 shows the lubricity after annealing when varying amounts of methyl methacrylate with a particle size of 25 nm were added as a heat-resistant coarse resin to a base liquid consisting of CrO + 100 g + MgO 20 g + fine particle acrylic-styrene resin emulsion. The measured results are shown.
第２図（ａ）は比較例としてベース液のみの場合、同図
（ｂ）〜（ｄ）はメチルメタアクリレートの添加量が５
ｇ、１０ｇ、２０ｇの場合の本発明例を示す。Figure 2 (a) is a comparative example where only the base liquid is used, and Figures (b) to (d) are when the amount of methyl methacrylate added is 5.
Examples of the present invention in the case of 10 g, 10 g, and 20 g are shown below.
潤滑特性は粗粒樹脂の添加量を増した場合が著しく良好
で、焼鈍後の表面突起が大きな影響を与えていることを
示している。The lubrication properties were significantly better when the amount of coarse resin added was increased, indicating that the surface protrusions after annealing had a large effect.
以上、本発明における構成要件の限定理由、効果等につ
いて述べてきたが本発明の処理液としては、前記の三つ
の主成分の他に、グリセリン等の還元剤や、硼酸、硼酸
塩等のガラス形成剤を加えても良い。The reasons for limiting the constituent elements, effects, etc. of the present invention have been described above. In addition to the three main components mentioned above, the processing liquid of the present invention also contains a reducing agent such as glycerin, and glass such as boric acid and borate. A forming agent may also be added.
実施例１
夫自体公知の方法で処理した板厚０．５閣の無方向性電
磁鋼板に表１に示す組成の耐熱性粗粒樹脂として粒子径
２０１ｒｍの粗粒子樹脂の添加量を変えた処理剤をゴム
ロールで塗布し、４５０″Ｃで３０秒間の焼き付け処理
を行った。この際の塗布量は乾燥、焼き付け後の重量で
１．５ｇ／ｎｆであった。Example 1 A non-oriented electrical steel sheet with a thickness of 0.5 mm treated by a method known per se was treated by changing the amount of coarse particle resin with a particle diameter of 201 rm as a heat-resistant coarse particle resin having the composition shown in Table 1. The agent was applied with a rubber roll and baked at 450''C for 30 seconds.The applied amount was 1.5 g/nf after drying and baking.
この鋼板からサンプルを切出し、７５０’ＣＸ２Ｈｒの
歪取焼鈍を行い、焼鈍時の鋼板のスティッキング状況、
焼鈍後の鋼板の表面粗さ、皮膜潤滑性、絶縁性、耐食性
等について調査を行った。A sample was cut from this steel plate and subjected to strain relief annealing at 750'CX2Hr, and the sticking condition of the steel plate during annealing was determined.
We investigated the surface roughness, film lubricity, insulation, corrosion resistance, etc. of the steel plate after annealing.
（１） スティッキング性試験方法
３ｃｍＸ４ｃｍに切断した鋼板を積層し、締付け圧力４
０ｋｇ／ｄで締付けた状態で７５０’ＣＸ２ＨｒＮ２中
で焼鈍を行った後の鋼板の剥離荷重を測定した。(1) Sticking test method Steel plates cut into 3cm x 4cm pieces were stacked, and a tightening pressure of 4 cm was applied.
The peeling load of the steel plate was measured after annealing in 750'CX2HrN2 with the steel plate tightened at 0 kg/d.
（２）密着性試験方法
焼鈍後の鋼板表面にセロハンテープを貼付け、セロハン
テープを剥がした時の皮膜の剥離状況を調査した。(2) Adhesion test method Cellophane tape was attached to the surface of the steel plate after annealing, and the peeling status of the film was investigated when the cellophane tape was peeled off.
（３）潤滑性試験方法
焼鈍後の鋼板表面に直径１０ｍ＋＋＋の鋼球を荷重１０
０ｇの条件で当て、往復運動させたときの滑り性（表面
抵抗）を測定した。(3) Lubricity test method A steel ball with a diameter of 10m+++ is applied to the surface of the steel plate after annealing with a load of 10
The slipperiness (surface resistance) when applied under the condition of 0 g and reciprocated was measured.
（４）耐食性試験方法
焼鈍後の鋼板を５Ｘ１０ｃｍに切断後、恒温湿気層中で
５０″Ｃｘ２４Ｈｒ（湿度９８％）の処理を行った後の
錆発生状況を調査した。(4) Corrosion resistance test method After cutting the annealed steel plate into 5 x 10 cm pieces, the steel plates were treated in a constant temperature humidity layer at 50 cm x 24 hours (humidity 98%), and the rust occurrence was investigated.
（５）層間抵抗試験方法 ＪＩＳ第二法によって測定した。(5) Interlayer resistance test method Measured by JIS second method.
この試験の結果、本発明によるものは焼鈍後の皮膜特性
として、耐ステイツキング性、潤滑性、耐食性、絶縁性
等がいずれも比較例に比し、著しく改善された結果が得
られた。As a result of this test, it was found that the film properties of the film according to the present invention after annealing, such as staking resistance, lubricity, corrosion resistance, and insulation properties, were all significantly improved compared to the comparative example.
また、この実験における比較例の特開昭６１１８３４７
９号公報記載のものは、粗粒樹脂を添加することでは本
発明と類似点はあるが、粗粒樹脂に耐熱性がないため、
本発明の様な焼鈍後の効果は全く生しなかった。Also, a comparative example in this experiment, JP-A No. 6118347,
The product described in Publication No. 9 has similarities with the present invention in that coarse grained resin is added, but since the coarse grained resin does not have heat resistance,
The effect after annealing as in the present invention was not produced at all.
実施例２
実施例１と同様にして、表３の如く無機−有機微粒子エ
マルジョン樹脂のベース組成液に対し、耐熱型粗粒子樹
脂を添加した処理剤をコーティングロールで塗布し、４
００ ’Ｃで６０秒間の焼き付け処理を行った。この際
の塗布量は焼き付け後の重量で１．５ｇ／ボであった。Example 2 In the same manner as in Example 1, a treatment agent containing heat-resistant coarse particle resin was applied to the base composition liquid of inorganic-organic fine particle emulsion resin as shown in Table 3 using a coating roll.
A baking process was performed at 00'C for 60 seconds. The amount of coating at this time was 1.5 g/bot after baking.
この鋼板からサンプルを切出し、７５０°ＣＸ２Ｈｒの
Ｎ２中歪取焼鈍を行った後、実施例１と同様にして皮膜
特性の調査を行った。A sample was cut out from this steel plate and subjected to strain relief annealing in N2 at 750°CX2Hr, and then the film properties were investigated in the same manner as in Example 1.
この試験の結果、本発明の処理剤を使用したものは、実
施例１と同様に、焼鈍後の皮膜特性が著しく改善された
結果が得られた。As a result of this test, similar to Example 1, in the case of using the treatment agent of the present invention, the film properties after annealing were significantly improved.
また、以上の実施例１，２では打抜き性、溶接性等の通
常の皮膜特性においても比較例と同等の結果を示し、問
題がなかった。Furthermore, in Examples 1 and 2, the results were comparable to those of the comparative example in terms of ordinary film properties such as punchability and weldability, and there were no problems.
（発明の効果）
本発明の処理方法においては、クロム酸塩−有機樹脂系
の処理液において、特定の耐熱型粗粒樹脂を添加配合す
ることにより、従来の皮膜特性を損なうことなく、従来
の有機−無機系皮膜の欠点であった焼鈍後の皮膜特性を
改善できる。(Effects of the Invention) In the treatment method of the present invention, by adding and blending a specific heat-resistant coarse-grained resin to the chromate-organic resin treatment solution, the conventional treatment method can be improved without impairing the conventional film properties. The film properties after annealing, which were a drawback of organic-inorganic films, can be improved.
特に、歪取焼鈍での皮膜の焼付きがなく、良好な磁気特
性が得られると共に、潤滑性、耐食性。In particular, there is no seizure of the film during strain relief annealing, and good magnetic properties are obtained, as well as lubricity and corrosion resistance.
絶縁性等の優れた絶縁皮膜を形成することが可能である
。It is possible to form an insulating film with excellent insulation properties.
第１図は耐熱型粗粒子樹脂の種類及び添加量と歪取焼鈍
後の表面粗さの関係を示す図、第２図は耐熱型粗粒子樹
脂の添加量と焼鈍後の皮膜潤滑性を示す図である。
案事璽
むFigure 1 shows the relationship between the type and amount of heat-resistant coarse particle resin added and the surface roughness after strain relief annealing, and Figure 2 shows the relationship between the amount of heat-resistant coarse particle resin added and the film lubricity after annealing. It is a diagram. consider matters
Claims (4)
Ｚｎから選ばれる酸化物の一種又は二種以上２０〜４０
重量部、粒子径０．２〜０．５μｍに調整したアクリル
，スチレン，酢酸ビニル及び／又はこれらの共重合体か
らなる樹脂の一種又は二種以上の微粒子エマルジョン溶
液１０〜６０重量部（固形分換算）、粒子径を１〜５０
μｍに調整したメチルメタアクリレート，ポリアクリル
ニトリル，ポリスチレン，スルホン化スチレン，セルロ
ーズ，シリコン，メラミン，フェノール，ポバールの樹
脂及び／又はこれらの共重合体、架橋体の一種又は二種
以上２〜３０重量部からなる電磁鋼板用表面処理剤。(1) CrO_3100 parts by weight, Al, Mg, Ca,
One or more oxides selected from Zn 20 to 40
10 to 60 parts by weight (solid content (conversion), particle size from 1 to 50
2-30% by weight of methyl methacrylate, polyacrylonitrile, polystyrene, sulfonated styrene, cellulose, silicone, melamine, phenol, poval resin and/or one or more copolymers or crosslinked products thereof adjusted to μm A surface treatment agent for electrical steel sheets consisting of parts.
Ｚｎから選ばれる酸化物の一種又は二種以上２０〜４０
重量部、Ａｌ，Ｍｇ，Ｃａから選ばれる第一燐酸塩の一
種又は二種以上５〜２５重量部、粒子径０．２〜０．５
μｍに調整したアクリル，スチレン，酢酸ビニル及び／
又はこれらの共重合体からなる樹脂の一種又は二種以上
の微粒子エマルジョン溶液１０〜６０重量部（固形分換
算）、粒子径１〜５０μｍに調整したメチルメタアクリ
レート，ポリアクリルニトリル，ポリスチレン，スルホ
ン化スチレン，セルローズ，シリコン，メラミン，フェ
ノール，ポバールの樹脂及び／又はこれらの共重合体、
架橋体の一種又は二種以上２〜３０重量部からなる電磁
鋼板用表面処理剤。(2) CrO_3100 parts by weight, Al, Mg, Ca,
One or more oxides selected from Zn 20 to 40
Parts by weight, 5 to 25 parts by weight of one or more primary phosphates selected from Al, Mg, and Ca, particle size 0.2 to 0.5
Acrylic, styrene, vinyl acetate and/or
Or 10 to 60 parts by weight (solid content equivalent) of a fine particle emulsion solution of one or more resins made of these copolymers, methyl methacrylate, polyacrylonitrile, polystyrene, sulfonated, adjusted to a particle size of 1 to 50 μm. Styrene, cellulose, silicone, melamine, phenol, poval resins and/or copolymers thereof,
A surface treatment agent for electrical steel sheets comprising 2 to 30 parts by weight of one or more crosslinked products.
最終焼鈍を行った鋼板上にクロム酸及び／又はクロム酸
塩の一種又は二種以上と有機樹脂からなる無機−有機系
皮膜の焼き付け処理を施す無方向性電磁鋼板の製造方法
において、ＣｒＯ＿３１００重量部、Ａｌ，Ｍｇ，Ｃａ
，Ｚｎから選ばれる酸化物の一種又は二種以上２０〜４
０重量部、粒子径０．２〜０．５μｍに調整したアクリ
ル，スチレン，酢酸ビニル及び／又はこれらの共重合体
からなる樹脂の一種又は二種以上の微粒子エマルジョン
溶液１０〜６０重量部（固形分換算）、粒子径１〜５０
μｍに調整したメチルメタアクリレート ポリアクリル
ニトリル，ポリスチレン，スルホン化スチレン，セルロ
ーズ，シリコン，メラミン，フェノール，ポバールの樹
脂及び／又はこれらの共重合体、架橋体の一種又は二種
以上２〜３０重量部からなる表面処理剤を塗布し、焼き
付け処理することを特徴とする歪み取り焼鈍時の耐焼付
き性が優れ、焼鈍後の潤滑性及び絶縁性の著しく優れる
無方向性電磁鋼板の製造方法。(3) Processing the material for non-oriented electrical steel sheet by a known method,
In a method for producing a non-oriented electrical steel sheet, in which a final annealed steel sheet is baked with an inorganic-organic film consisting of one or more chromic acid and/or chromate salts and an organic resin, CrO_3100 parts by weight , Al, Mg, Ca
, one or more oxides selected from Zn 20-4
0 parts by weight, 10 to 60 parts by weight of a fine particle emulsion solution of one or more resins made of acrylic, styrene, vinyl acetate and/or their copolymers adjusted to a particle size of 0.2 to 0.5 μm (solid) minute conversion), particle size 1 to 50
Methyl methacrylate adjusted to μm 2 to 30 parts by weight of polyacrylonitrile, polystyrene, sulfonated styrene, cellulose, silicone, melamine, phenol, poval resin and/or one or more copolymers or crosslinked products thereof A method for producing a non-oriented electrical steel sheet which has excellent seizure resistance during strain relief annealing and has extremely excellent lubricity and insulation properties after annealing, the method comprising applying a surface treatment agent consisting of: and baking treatment.
最終焼鈍を行った鋼板上にクロム酸及び／又はクロム酸
塩の一種又は二種以上と有機樹脂からなる無機−有機系
皮膜の焼き付け処理を施す無方向性電磁鋼板の製造方法
において、ＣｒＯ＿３１００重量部、Ａｌ，Ｍｇ，Ｃａ
，Ｚｎから選ばれる酸化物の一種又は二種以上２０〜４
０重量部、Ａｌ，Ｍｇ，Ｃａから選ばれる第一燐酸塩の
一種又は二種以上５〜２５重量部、粒子径０．２〜０．
５μｍに調整したアクリル，スチレン，酢酸ビニル及び
／又はこれらの共重合体からなる樹脂の一種又は二種以
上の微粒子エマルジョン溶液１０〜６０重量部（固形分
換算）、粒子径１〜５０μｍに調整したメチルメタアク
リレート，ポリアクリルニトリル，ポリスチレン，スル
ホン化スチレン，セルローズ，シリコン，メラミン，フ
ェノール，ポバールの樹脂及び／又はこれらの共重合体
、架橋体の一種又は二種以上２〜３０重量部からなる表
面処理剤を塗布し、焼き付け処理をすることを特徴とす
る歪み取り焼鈍時の耐焼付き性が優れ、焼鈍後の潤滑性
及び絶縁性の著しく優れる無方向性電磁鋼板の製造方法
。(4) Processing the material for non-oriented electrical steel sheet by a known method,
In a method for producing a non-oriented electrical steel sheet, in which a final annealed steel sheet is baked with an inorganic-organic film consisting of one or more types of chromic acid and/or chromates and an organic resin, CrO_3100 parts by weight , Al, Mg, Ca
, one or more oxides selected from Zn 20-4
0 parts by weight, 5 to 25 parts by weight of one or more primary phosphates selected from Al, Mg, and Ca, particle size 0.2 to 0.
A fine particle emulsion solution of one or more resins made of acrylic, styrene, vinyl acetate, and/or their copolymers adjusted to 5 μm, 10 to 60 parts by weight (in terms of solid content), adjusted to a particle size of 1 to 50 μm Surface consisting of 2 to 30 parts by weight of methyl methacrylate, polyacrylonitrile, polystyrene, sulfonated styrene, cellulose, silicone, melamine, phenol, poval resin and/or one or more of these copolymers or crosslinked products A method for producing a non-oriented electrical steel sheet, which has excellent seizure resistance during strain relief annealing and has extremely excellent lubricity and insulation properties after annealing, the method comprising applying a treatment agent and performing baking treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3475390A JP2762147B2 (en) | 1990-02-15 | 1990-02-15 | Method for producing non-oriented electrical steel sheet with excellent film properties after strain relief annealing and surface treating agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3475390A JP2762147B2 (en) | 1990-02-15 | 1990-02-15 | Method for producing non-oriented electrical steel sheet with excellent film properties after strain relief annealing and surface treating agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03240970A true JPH03240970A (en) | 1991-10-28 |
| JP2762147B2 JP2762147B2 (en) | 1998-06-04 |
Family
ID=12423084
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3475390A Expired - Lifetime JP2762147B2 (en) | 1990-02-15 | 1990-02-15 | Method for producing non-oriented electrical steel sheet with excellent film properties after strain relief annealing and surface treating agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2762147B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06235070A (en) * | 1993-02-08 | 1994-08-23 | Kawasaki Steel Corp | Silicon steel sheet having electrically insulated film excellent in weldability |
| JP2003526727A (en) * | 2000-03-16 | 2003-09-09 | ポーハング アイアン アンド スティール シーオー．，エルティディ． | Coating composition for forming insulating film, non-oriented electrical steel sheet coated with the coating composition, and method for forming insulating film on the steel sheet |
| WO2011033943A1 (en) | 2009-09-15 | 2011-03-24 | 新日本製鐵株式会社 | Electromagnetic steel sheet and method for producing same |
-
1990
- 1990-02-15 JP JP3475390A patent/JP2762147B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06235070A (en) * | 1993-02-08 | 1994-08-23 | Kawasaki Steel Corp | Silicon steel sheet having electrically insulated film excellent in weldability |
| JP2003526727A (en) * | 2000-03-16 | 2003-09-09 | ポーハング アイアン アンド スティール シーオー．，エルティディ． | Coating composition for forming insulating film, non-oriented electrical steel sheet coated with the coating composition, and method for forming insulating film on the steel sheet |
| WO2011033943A1 (en) | 2009-09-15 | 2011-03-24 | 新日本製鐵株式会社 | Electromagnetic steel sheet and method for producing same |
| US10340065B2 (en) | 2009-09-15 | 2019-07-02 | Nippon Steel & Sumitomo Metal Corporation | Method for manufacturing electrical steel sheet |
| EP3836169A1 (en) | 2009-09-15 | 2021-06-16 | Nippon Steel Corporation | Electrical steel sheet and method for manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2762147B2 (en) | 1998-06-04 |
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